Method for the production of sulphonic acids



Patented July 10, 1934 UNITED STATES PATENT OFFICE METHOD FOR THE PRODUCTION OF SULPHONIC ACIDS Erik Schirm, Dessau,

Germany, assignor, by

mesne assignments, to Unichcm Chemikalicn Handels A.-G., Zurich, Switzerland, as corporation oi Switzerland No Drawing. Application December 22, 1931, Serial No. 582,646. In Germany December 23,

' 24 Claims.

This invention relates to sulphonic acids useful as wetting-out, emulsifying, dispersing, pep-- tizing and cleansing agents and methods of producing the same.

It has been found, that excellent wetting-out-, emulsifying, dispersing-, peptizationcleansing agents are obtained by converting mineral acid esters or estersalts, for instance the halogen hydracid ester or sulphuric acid ester salts of higher molecular monoor polyvalent aliphatic or hydrocyclic alcohols with at least one primary alcohol group, such as may be obtained from natural waxes by splitting off or reduction. (hydrogenation) or from natural fats, iattyacids 25 phone acid by oxidation of, cetylmer'captane with potassium permanganate. This process however in comparison with the present inventon is a very expensive and indirect one as in spitelof greater expenses for chemicals, apparatus and time rather go unsatisfactory yields only could be obtained. That is Why this process hitherto has not been carried out practically. Furthermore is it already known that the cetylsulphonic acid has some soaplike properties, theprior art however does not contain the new knowledge, that the sulphonc acids of the aliphatic or hydrocyclic rank with a sulphonc acid group attached to the .end carbon atom of the chain, are far superior as regards the capillary activity to the corresponding 40 soap forming carboxylic acids and also to other sulphonic acids. The production therefore of aliphatic or hydrocyclic sulphonic acids having the sulpho-group at the end of the chain, by a process which can be carried out technically and commercially without difi'iculty as herein described constitutes industrial progress.

Theproducts obtained in accordance with the present invention contain the sulphonic acid group at the end of the chain only whereby as regards the capillary activity they far surpass all other substances used according to hitherto proposed methods for the production of wetting-out, emulsifying and dispersing agents.

This fact was unknown hitherto and had therefore not been taken into consideration in the and known processes of producing sulphonic acids for the. purposes of wetting-out, emulsifying and similar purposes. In contrast with other processes,

which are based for instance on the conversion.

of mineral acid esters of alcohols with neutral salts of sulphurous acid yielding also compounds with the sulpho-group at the end of the chain, the present invention shows the following advantages: 'I'he alkali polysulphides are distinguished from the alkali sulphides by 'a considerably increased reaction-energy; therefore it is possible to operate the conversions under milder conditions regarding pressure and temperature, as is evident from the following examples. Furthermore by this method also side-reactions, as

for instance saponification of the esters or estersalts are avoided'and the addition of expensive reaction-accelerators, as for instance alkali iodides, which have to be regenerated, can be dispensed with.

The oxidation of the disulphides obtained as intermediate products to the sulphonic acids can be carried out by various means. As suitable agents we have found for instance free halogens,

hypohalogenous acids and their salts, halogenates (sodium-chlorate) in the presence of traces of 'osmiumtetroxide, free chloric acid,

hydrogen peroxide and its inorganic or organic derivatives (as for instance .persulphuric acid.

erably in acid solution. All these oxidizing agents may be applied in aqueous solution with or without the addition of known catalyst. v In case oxidizing agents are used which react with evolution of gas, foaming compounds may be yielded if the oxidation is carried .on in aqueous solution. For this reason it is recommended that there should be added to the medium in which the oxidation is carried on such substances as destroy either wholly or partially the colloidal nature of the resulting sulphonic acids and which are able to convert these sulphonic acids more or less into a molecularly dispersed state. Such substances, which of course must to be inert to the oxidizing agent usedin the special case, are for instance methyl alcohol, acetone, acetic acid.

Example I "ie di acid, nitric acid of various concentration,

this are cooked under reflux at ordinary pressure, I together with a concentrated aqueous solution of 43 parts of sodium-sulphide (NazS) and 18 parts of sulphur after 300350 parts of alcohol are added until after'about 2-3 hours the conversion is completed. The alcohol then is distilled oil, the residue diluted with water and the dicetyldisulphide, which is already at slight warth oleaginous is decanted from the watery layer. After cooling it solidifies to a white waxy mass.

, The disulphide is suspended in warm, dilute sulphuric acid, so that it is just molten, and then gradually while stirring vigorously a 5% solution of sodium permanganate is added until the violetcolor persists. The resulting sodium 'salt of cetylsulphonic acid'is extracted by means of butylalcohol and upon evaporating the latter-it is yielded in a solid form. Or the oxidation mixture is evaporated to dryness and the sodium salt of cetyl-sulphonic acidis extracted with alcohol.

Example II A mixture of higher aliphatic primary alcohols,

such asis obtained by catalytic high pressure hydrogenation of coconut oil or mixture of coconut oil fatty acids or by reduction with sodium and alcohol, is convertedto the corresponding alkyl sulphuric acids in the usual manner with chlorsulphonic acid at low temperatures. These are introduced into the calculated quantity of 40% caustic soda lye while stirringand with orW'ithresidue isrefliled with some sulphuric acid, neuout cooling and to the resulting paste are added a quantity of alcohol, approximately equal to the water present and a concentrated solution of potassium trisulphide about in excess of 10% over the theoretically necessary amount. The mixture is then heated in a stirring autoclave to 150 C. until all the sulphuric acid of the estersalts is split off in the form of sodium-sulphate, the alcohol is distilled oil and the oily trisulphide mixture is separated from the watery layer.

Twice the amount of 20% nitric acid as the! oretical necessary for the quantitative oxidation of the trisulphide mixture is heated up to C. and to this is added at intervals, while stirring, the trisulphide mixture, waiting each time until the brisk reaction, which proceeds with foaming, subsides before adding another portion of the trisulphide mixture After the whole mass is introduced, it is necessary to start at 85 to 95 C. until a sample of the reaction mixture gives a clear solution in water and dilute alkali lye. It is then neutralized with caustic soda lye and extracted with butylalcohol. The butylalcoholic layer is dcated and upon evaporation yields a mixture of the sodium salts of higher alkylsulphonic acids. From the watery layer sodium nitrate may be obtained.

Example. III

A mixture 'or naphthenic alcohols boiling at about -125 C. under 15 mm. Hg pressure as obtained for instance by reduction of naphthenic acids with sodium and butylalcohol according to the method of Blanc and Bouveault, is heated up to 150 C. 1% dry zinc chloride is added and a vigorous stream of dry hydrochloric gas is passed through until no more water distills oil. The raw naphthenylchloride which remains as tralizedbywashing, dried and distilled in vacuum. 116.4 parts of the resulting chloride boiling point at 13 minus-200 c. with 15.22% chlorine contents are added to .a boiling solution of 35.8

parts of sodium. sulphide (techn. cone. with 60-62% Nags) and 11 parts of sulphur in 150 parts90% alcohol. This mixture is kept'boiling I duced into a mixture, which is kept continuously at,55-60, of 100 parts of glacial aceticacid;

100 parts of water and 125 parts of 60-62% nitric acid, to which 1 part of ammonium metavanadate is added. Then the reaction mixtureis heated up for some time to 75-80 C. until no action more can be observed,. and the watery acetic aciddistilled oil under vacuum, the residue dissolved in water and neutralized with caustic soda lye. The solution is evaporated to dryness, perferably in vacuum, and the dry residue is extracted with benzene, benzine or other fat solvents, in order to remove water insoluble by products. The sodium salts of the naphthenylsulphonic acids remain as dry yellowish-white powder, which is easily soluble in cold as well as in warm water and .which possesses in these solutions an extraordinarily high wetting-out and penetrating power and. also high lathering capacity. Also calcium and magnesium salts in higher concentrations cause no precipitation- The product is furthermore, as real sulphonic acid, wholly stable to- Wards acids and alkalies and therefore constitutes a rather valuable soap body particularly .suitable for use in the textile, leather-, paperandhll other industries, in whichit is essential to produce the especially importanntechnically valuable capillaractive properties of these compounds together with a general chemical stability.

Example IV the salt lye and stirred with four times the quantity oi acetic acid 50%, to which some concentrated hydrochloric acid is added. The whole is heated up in a waterbath and during active stirring about 180 parts of sodium chlorate are introduced in small portions until after some further stirring a complete water and alkali-solubility of the reaction mixture is arrived at. Now

the reaction mixture is salted out with Glaubers salt (sodium sulphate) and the sodium salt of dodecylsulphonic acid precipitated in crystals is vacuum drained and refined by recrystallizing with water. An excellent wetting-out and emulsilying product is yielded.

I claim:

I 1. Theprocess of producing high molecular sulphonic acids or sulphonates which comprises converting-alcohols of the group consisting of monoand poly-hydroxy aliphatic alcohols obtained from natural fats and waxes and having 8 or more carbon atoms inthe molecule a naph thenic acidinto miners-lucid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides and converting the polysulphides into products of the group consisting of sulphomc acids and sulphonates by oxidation. I

2. The process of producing high molecular sulphonic. acids or sulphonates which'comprises converting high molecular alcohols of the group consisting of the monoand poly-hydroxy .aliphatic alcohols obtained from natural fats and waxes, and naphthenic alcohols, into mineral acid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides at elevated temperatures and convertlng the polysulphides into products of the group consisting of sulphonic acids and sulphonates byoxidation.

3. The product resulting from the process defined in claim 2.

4. The process of producing high molecular sulphonic acids or sulphonates which comprises converting aliphatic alcohol obtained from natural fats and waxes into mineral acid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides at elevated temperatures and converting the polysulphides into products of the group consisting of sulphonic acids and sulphonates by treatment with an oxidizing agent of the group consisting of free halogens, hypohalogenous acids and their salts and halogenates.

5. The product resulting from the process deural fats and waxes into mineral acid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides at elevated temperatures and converting the polysulphides into products of the group consisting of'sulphonic acids and sulphonates by treatment with an oxidizing agent of the group consisting of free halogens, hypohalogenous acids and. their salts and halogenates in the presence of material selected from the group consisting of osmium tetroxide, free chloric acid, iodic acid, nitric'acid, hydrogen peroxide and its organic and inorganic derivatives, chromic acid and chromates in acid solution, and permanganates'. Y

7. The process of producing high molecular sulphonicacids or sulphonates which comprises converting aliphatic alcohol obtained from natural fats and waxes into mineral acid esters by treatment with an acidof the group consisting of hydrochloric acid, sulphuric acid, nitric acid, converting the mineral acid esters intoorganic polysulphides and converting the. polysulphides into products of the group consisting of sulphonic acids and sulphonates.

8. The product resulting from the process defined in claim 7. i

9. In the process ofproducing high ular' alcohols'of the group consisting of the mono,-

and ,poly-hydroxy aliphatic alcohols obtained from natural fats and waxes, and naphthenic alcohols, the step which consists of converting mineral acid esters of such high molecular alcohols alkalipolysulphid into organic polysulphides by treatment with 10. In the'proces's of. producing high molecular sulphonic acids or sulphonates from high molecular alcohols'of the group consisting of the monoand poly-hydroxy aliphatic alcohols obtained from natural fats and waxes, and naphthenic Ialcohols, the .step which consists of converting mineral acid .esters oisuch high molecular alcohols into organic polysulphides by treatment with molecular sulphonic acids or sulphonates from high molecalkali polysulphides of the group consisting of sodium polysulphide and potassium polysulphide.

11. In the process of producing high molecular sulphonic acids or sulphonates, the step which consists of converting an alkyl chloride having 8 or more carbon atoms in the molecule into a dialkyl disulphide by boiling with sodium sulphide and sulphur at an elevated temperature with ,re-

12. In the process of producing high molecular sulphonic acids or sulphonates, the step which consists of converting an alkyl polysulphide into a product of the group consisting of sulphonic acids and sulphonates by suspension in warm sulphuric acid of alkyl polysulphide having 8 or more carbon atoms in the alkyl group and reaction with an oxidizing agent.

13. In the process of producing high molecular sulphonic acids or sulphonates, the step which consists of converting a di-alkyl disulphide into a product of the group consisting of sulphonic acids and sulphonates by treatment of a di-alkyl disulphide having 8 or more carbon atoms in the alkyl group with an oxidizing agent of the group consisting of free halogens, hypohalogenous acids and their salts and halogenates. 4

14. In the process of producing high molecular sulphonic acids or sulphonates, the step which consists of converting an alkyl polysulphide into a product of the group consisting of sulphonic acids and sulphonates by treatment of analkyl polysulphide having 8 or more carbon atoms in the alkyl group with an oxidizing agent of the group consisting of free halogens, hypohalogenous acids and their salts and halogen-ates in thepresence of materials of the group consisting of osmium tetroxide, free chloric acid, iodic acid, nitric acid, hydrogen peroxide and its organic and inorganic derivatives, chromic acid and chromates in acid solution and permanganates.

15. In the process of producing high molecular sulphonic acids or sulphonates, the step which consists of converting an alkyl polysulphide into sodium sulphonate by treatment of an alkyl poly-' sulphide having 8 or more carbon atoms in the. alkyl group with sodium permanganate in the presence of warm sulphuric acid as a diluent.

16. In the process of producing high molecu- I lar sulphonic acidsor sulphonates, the step which 5 consists of converting an alkyl polysulphide into a product of the group consisting of sulphonic acids and sulphonates by treatment of an alkyl polysulphide having 8 or more carbonatoms in the alkyl group with an oxidizing agent in the 130 presence of an agent of the groupconsisting of methyl alcohol, acetone and acetic acid.

17. In the process of producing high molecular sulphonic acids or sulphonates from high molecular alcohols the step which consists of react- 135 ing an alkali sulphate of a high molecular monohydroxy aliphatic alcohol with-polysulphide of the group consisting of sodium polysulphide and potassium polysulphide. v

18. The process of producing high molecular sulphonic acids or sulphonates which comprises converting alcohols of the group consisting of monoand poly-hydrozw aliphatic alcohols obtained from natural fats and waxes and having 8 145 or more. carbon atoms in the molecule into chlorides by treatment with hydrochloric acid, converting the chloride into organic disulphides ,by treatment with sodium sulphide and sulphur the group consisting of sulphonic acid and sul phonats by oxidation while suspended in warm dilute sulphuric acid.

19, The process of producing high molecular sulphonic acids or sulphonates which comprises converting alcohols of the group consisting of monoand poly-hydroxy aliphatic alcohols obing the naphthenic sulphide into sulphonic acid by oxidizing with nitric acid.

21. The process of producing molecular sulphonic acids or sulphonates which compr'mes converting .dodecyl bromide into disulphide by treatment with sodium disulphide with refluxing and converting the dodecyl disulphide into sodium sulphonate by treatment with sodium chlorate.

22. The proces of producing high molecular sulphonic acids and sulphonates which comprises converting aliphatic monhydroxy alcohols having approximately 12 to 16 into mineral acid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides at elevated temperatures and converting the polysulphides into products of the group consisting of 'sulphonic acids and sulphonates by oxidation.

23. The product resulting from the process defined in claim 22.

24. The process of producing high molecular sulphonic acids and sulphonates which comprises converting aliphatic monhydroxy alcohols having approximately 12 to 16 into mineral acid esters, converting the mineral acid esters into organic polysulphides by treatment with alkali polysulphides at elevated temperatures and converting the polysulphides into products of the group consisting of sulphonic acids and sulphonates by treatment with an oxidizing agent of the group consisting of free halogens, hypohalogenous acids and their salts, and halogenates in thepresence of an oxidation catalyst.

ERIK SCEIRM.

its 

